This article gives a comprehensive review of the synthetic development of centrohexacyclic organic compounds (''centrohexacyclanes'') during the past decade. With their unique feature of having molecular constitution that corresponds to the complete graph K-5, centrohexacyclanes represent the majority of the rare class of topologically nonplanar compounds. Starting from the few previously known organic, element-organic and inorganic K-5 compounds, the syntheses of various organic centrohexacyclanes are discussed, based mainly on three different strategies that have emanated from the chemistry of centropolyindanes: the propellane, fenestrate, and ''broken fenestrane'' routes. In addition, the first results of some targeted transformations of centrohexaindane, the T-d-symmetrical hexabenzoannelated centrohexaquinane, are presented.